Method for producing a syngas stream

ABSTRACT

The present invention provides a method for producing a syngas stream, the method at least comprising the steps of: (a) providing a hydrocarbon-containing stream; (b) providing a reactor containing a heated mass of solids at a temperature of at least 1000° C.; (c) cracking the hydrocarbon-containing stream provided in step (a) in the reactor containing the heated mass of solids provided in step (b), thereby at least obtaining C and H2; (d) removing an H2-containing stream from the reactor; (e) converting the C obtained in step (c) in the reactor at an H2O/CO2 vol. % feed ratio of greater than zero, thereby obtaining a CO/H2-containing stream; (f) removing the CO/H2-containing stream from the reactor; (g) combining the H2-containing stream removed in step (d) with the CO/H2-containing stream removed in step (f) thereby obtaining a syngas stream.

PRIORITY CLAIM

The present application is the National Stage (§ 371) of InternationalApplication No. PCT/EP2015/065332, filed Jul. 6, 2015, which claimspriority from European Patent Application No. 14176091.8, filed Jul. 8,2014 incorporated herein by reference.

The present invention relates to a method for producing a syngas stream,in particular a non-catalytic method. Various methods for producing asyngas stream are known in the art.

An example of a non-catalytic method for producing syngas is disclosedin GB 2 265 382.

A problem of the method as disclosed in GB 2 265 382 is that the ratioof the H₂ and CO in the produced syngas is fixed (3:1; i.e. a H₂/CO vol.% ratio of 3.0). This fixed H₂/CO vol. % ratio is not always suited forsubsequent processing, such as for Fischer-Tropsch reactions.

GB 365 912 (published in January 1932) relates to the manufacture ofcombustible gas rich in hydrogen by the pyrogenous decomposition ofhydrocarbons by passing hydrocarbons through an ignited bed of solidfuel such as coal. The natural gas as used in the example which ispassed through the fuel bed contains 17.6% C₂H₆, 75.0% CH₄, 0.4% CO₂,0.2% O₂ and 6.8% N₂, but no mercaptans. Furthermore, the bed of solidfuel is ignited to provide the heat for the pyrogenous decomposition ofthe hydrocarbons. That implies the fuel bed is consumed and need to bereplaced when it can no longer provide the necessary heat for thedecomposition of hydrocarbons.

EP 0 219 163 A2 (published in April 1987) relates to a process forproducing a hydrogen-containing gas which comprises the following steps:

(i) cracking hydrocarbonaceous material substantially in the absence ofsteam into carbon and hydrogen-containing gas by contacting saidmaterial with a heated mass of non-fluidized solids and allowing carbonto deposit on the solids; and

(ii) steam gasification of carbon formed in step (i). EP 0 219 163suggests to subject natural gas to a treatment to remove sulphur and/orinorganic substances before using it as a feed for the process. Nospecific mention of mercaptans is made in EP 0 219 163. Furthermore,there is no mention of any carbon dioxide being used in the steamgasification step to convert carbon formed into carbon monoxide.

It is an object of the present invention to overcome or minimize theproblem of a fixed ratio of H₂ and CO in the produced syngas to havemore options for further processing, e.g. in Fischer-Tropsch reactions.More generally, it is an object of the present invention to provide analternative method for producing a syngas stream, in particular anon-catalytic method, which method allows to obtain a flexible H₂/COvol. % ratio of the produced syngas.

It is another object of the present invention to provide an alternativemethod for producing a syngas stream, in particular a non-catalyticmethod, which uses a bed of solid materials which can be used for longerperiods of time without being consumed.

It is a further object of the present invention to provide a methodwhich allows to process a hydrocarbon-containing stream that containsmercaptans, without the need for amine treating or other separation toremove mercaptans before converting the hydrocarbon-containing streaminto syngas.

One or more of the above or other objects can be achieved by providing amethod for producing a syngas stream, the method at least comprising thesteps of:

-   (a) providing a hydrocarbon-containing stream;-   (b) providing a reactor containing a heated mass of solids at a    temperature of at least 1000° C.;-   (c) cracking the hydrocarbon-containing stream provided in step (a)    in the reactor containing the heated mass of solids provided in step    (b), thereby at least obtaining C and H₂;-   (d) removing an H₂-containing stream from the reactor;-   (e) converting the C obtained in step (c) in the reactor at an    H₂O/CO₂ vol. % feed ratio of greater than zero, thereby obtaining a    CO/H₂-containing stream;-   (f) removing the CO/H₂-containing stream from the reactor;-   (g) combining the H₂-containing stream removed in step (d) with the    CO/H₂-containing stream removed in step (f) thereby obtaining a    syngas stream.

It has surprisingly been found that the method according to the presentinvention allows to produce a syngas stream with a flexible H₂/CO vol. %ratio in a surprisingly simple manner. An important advantage of thepresent invention is that CO₂ can be used to produce the CO; usually itis very difficult to ‘reform’ CO₂ with e.g. CH₄ into CO/H₂ in view ofcarbon formation on (cracking) catalysts. A further advantage accordingto the present invention is that no catalysts need to be used forcracking. As a consequence, the method according to the presentinvention can also be used for hydrocarbon-containing streams containingH₂S and mercaptan compounds (which typically need to be removed in caseof catalytic methods for producing syngas to prevent poisoning of thecatalyst). Further, the hydrocarbon-containing stream to be used in thepresent invention is not critical with respect to amounts of olefins andthe like; the hydrocarbon-containing stream may contain higher amountsthereof which would otherwise result in poisoning of the catalysts.Also, no expensive amine treating units or the like are needed to treatthe stream provided in step (a) to remove any mercaptans before crackingin step (c).

A further advantage according to the present invention is that there isno need for an ASU (Air Separation Unit) as no high purity O₂ isrequired; this makes the method suitable for applying in small-scaleoperations.

In step (a), a hydrocarbon-containing stream is provided. Thishydrocarbon-containing stream is not limited in any way and may benatural gas, associated gas, crude oil and the like. Typically thehydrocarbon-containing stream is a hydrocarbon-containing gas stream,preferably containing at least 30 vol. % methane.

As mentioned above, the method according to the present invention issuited for hydrocarbon-containing streams that contain some contaminantsthat are not desired in case of catalytic methods for producing syngas.Hence, in a preferred embodiment of the present invention, thehydrocarbon-containing stream provided in step (a) comprises at least 10ppm mercaptans (such as—but not limited to—methanethiol (CH₃SH),ethylmercaptan (C₂H₅SH) and propylmercaptan (C₃H₇SH)), preferably atleast 50 ppm, more preferably at least 80 ppm. Furthermore, in anotherembodiment according to the present invention, thehydrocarbon-containing stream provided in step (a) comprises at least1.0 vol. %, at least 2.0 vol. %, at least 3.0 vol. % or even at least5.0 vol. % olefins.

In step (b), a reactor is provided that contains a heated mass of solidsat a temperature of at least 1000° C. The person skilled in the art willreadily understand that the heated mass of solids may be varied broadly.As an example, the heated mass of solids may be in the form of fixedbeds containing heat-resistant solid material in any desired shape andsize, such as a fixed brick matrix or a packed bed of particulatesolids. Various solid materials may be used in the method according tothe present invention; suitable solid materials comprise inert ceramicmaterials, refractory oxides (e.g. aluminium oxide, yttrium oxide,zirconium oxide), silicium carbide, carbonaceous materials, metal alloysand metal compounds, etc. The increased temperature of the heated massof solids may be obtained in various ways.

In step (c), the hydrocarbon-containing stream provided in step (a) iscracked in the reactor containing the heated mass of solids provided instep (b), thereby at least obtaining C (carbon) and H₂ (hydrogen).Typically, the C obtained in step (c) is deposited on the heated mass ofsolids in the reactor.

Preferably, the reactor containing the heated mass of solids is in step(c) at a temperature of at least 1100° C., preferably at least 1200° C.,more preferably at least 1350° C. and at most 1500° C., preferably atmost 1400° C. Typically, the cracking in step (c) is performed at apressure in the range from 0.5 to 50 bara, preferably from 5 to 20 bara.As the person skilled in the art is familiar with (non-catalytic)cracking, this is not further discussed here in detail.

In step (d), an H₂-containing stream is removed from the reactor.Preferably, the H₂-containing stream removed from the reactor in step(d) comprises at least 1 ppm H₂S, preferably at least 2 ppm, which is atleast partially removed before combining in step (g) thereby obtainingan H₂S-depleted H₂-containing stream. Preferably, the H₂S-depletedH₂-containing stream contains less than 0.1 ppm H₂S. As the personskilled in the art is familiar with the removal of H₂S from a stream(e.g. using molsieves, amines, etc.), this is not further discussed herein detail.

Further, it is preferred that a part of the H₂-containing stream removedfrom the reactor in step (d) is used to heat the reactor, such as bycombustion thereof. It goes without saying that part(s) of theH₂-containing stream removed from the reactor in step (d) may also beused for other uses such as hydrotreating, hydrocracking, etc.

In step (e), the C obtained in step (c) is converted in the reactor atan H₂O/CO₂ (water/carbon dioxide) vol. % feed ratio of greater thanzero, thereby obtaining a CO/H₂-containing stream. The person skilled inthe art will understand that the CO/H₂-containing stream as obtained instep (e) is a syngas stream; however, in order not to confuse the syngasstream as obtained in step (e) with the (H₂-enriched) syngas stream asobtained in step (g), the syngas stream as obtained in step (e) will becalled “the CO/H₂-containing stream” herein. As the person skilled inthe art is familiar with the kind of conversion as occurring in step(e), this is not further discussed here in detail. Typically, aCO₂-containing stream and/or steam is (are) fed to the reactor forobtaining the desired H₂O/CO₂ vol. % ratio in step (e); in the lattercase the H₂O/CO₂ vol. % ratio is also the H₂O/CO₂ vol. % feed ratio. Inan especially preferred embodiment the CO₂-containing stream is recycledfrom elsewhere in the process line-up or is obtained as an exhauststream from a nearby process line-up; this advantageously results in alowering of overall CO₂ footprint. Alternatively or additionally, thehydrocarbon-containing stream provided in step (a) contains CO₂.

Preferably, the reactor containing the heated mass of solids is in step(e) at a temperature of at least 1000° C., preferably at least 1100° C.,more preferably at least 1200° C. and at most 1500° C., preferably atmost 1400° C. Further, the conversion in step (e) is performed at apressure in the range from 0.5 to 50 bara, preferably from 5 to 20 bara.

Further its is preferred that in step (e) the C obtained in step (c) isconverted in the reactor at an H₂O/CO₂ vol. % feed ratio of at least0.0001, preferably at least 0.001, more preferably at least 0.5, evenmore preferably at least 0.9, yet even more preferably at least 1.2 andat most 1000, preferably at most 100, more preferably at most 10, evenmore preferably at most 3.0, yet even more preferably at most 2.5 andmost preferably at most 2.2. Preferably, in step (e) the C obtained instep (c) is contacted with steam.

In step (f), the CO/H₂-containing stream is removed from the reactor.

In step (g), the H₂-containing stream removed in step (d) is combinedwith the CO/H₂-containing stream removed in step (f) thereby obtaining asyngas stream. Typically, the syngas stream obtained in step (g) has aH₂/CO vol. % ratio of between 0.5 and 5.0, usually above 0.9 and below3.5. Preferably, the syngas stream obtained in step (g) has a H₂/CO vol.% ratio of at least 1.0 and below 3.1, preferably at least 1.6, morepreferably at least 1.75 and preferably at most 2.2, more preferably atmost 2.05.

Hereinafter the invention will be further illustrated by the followingnon-limiting example.

EXAMPLES

In these calculated Examples (using HSC chemistry software, availablefrom Outokumpu Research OY, Pori, Finland), a natural gas feed stream isused containing methane, nitrogen, 0.01 vol. % (i.e. 100 ppm)methanethiol (CH₃SH; a mercaptan that is typically present in naturalgas) and 0.01 vol. % (i.e. 100 ppm) ethylmercaptan (C₂H₅SH).

The above natural gas feed stream is cracked in a reactor containing aheated mass of solids at an elevated temperature thereby obtaining C(deposited on the heated mass of solids) and H₂. The H₂-containingstream is removed from the reactor and subjected to amine treating toremove the H₂S (formed in the reactor by conversion of the CH₃SH andC₂H₅SH into H₂S, H₂ and C).

The composition of the above natural gas feed stream and the removedH₂-containing stream as well as the cracking conditions are given forExamples 1-8 in Table 1 below.

TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 Ex. 8 Composition ofnatural gas feed stream CH₄ [vol. %] 99.87 99.87 99.87 99.87 94.87 94.8794.87 94.87 N₂ [vol. %] 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 H₂S [vol. %]0.01 0.01 0.01 0.01 0.01 0.01 0.01 0.01 CH₃SH [vol. %] 0.01 0.01 0.010.01 0.01 0.01 0.01 0.01 C₂H₅SH [vol. %] 0.01 0.01 0.01 0.01 0.01 0.010.01 0.01 C₂H₄ [vol. %] — — — — 5 5 5 5 Cracking properties Pressure[bara] 10 10 1 1 10 10 1 1 Temperature [° C.] 1300 1200 1300 1200 13001200 1300 1200 Composition of H₂-containing stream CH₄ [vol. %] 1.832.83 0.2 0.3 1.83 2.83 0.2 0.3 N₂ [vol. %] 0.05 0.05 0.05 0.05 0.05 0.050.05 0.05 H₂S [vol. %] 0.015 0.015 0.015 0.015 0.015 0.015 0.015 0.015CH₃SH [vol. %] — — — — — — — — C₂H₅SH [vol. %] — — — — — — — — C₂H₄[vol. %] — — — — — — — — H₂ [vol. %] balance balance balance balancebalance balance balance balance

The C obtained (as deposited on the heated mass of solids) is convertedin the reactor at a specific H₂O/CO₂ vol. % ratio (tuned by theinjection of CO₂ and H₂O) thereby obtaining a CO/H₂-containing stream,which is subsequently removed from the reactor. The CO/H₂-containingstream is subsequently combined with a H₂-containing stream (cf.Table 1) thereby obtaining a syngas stream. In these calculatedExamples, such H₂-containing stream was assumed to contain about 99 vol.% H₂. The H₂/CO vol. ratio of the syngas stream has been given in Table2.

Table 2 below lists some Examples (Examples 9-20) with differentconversion conditions and/or H₂O/CO₂ vol. % feed ratios for the streamfed to (by H₂O en CO₂ injection) and to be converted in the reactor.

The person skilled in the art will readily understand that manymodifications may be made without departing from the scope of theinvention.

TABLE 2 Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Ex. 17Ex. 18 Ex. 19 Ex. 20 Composition of stream to be converted in reactorCO₂ [vol. %] 99.80 99.80 99.80 99.80 49.95 49.95 49.95 49.95 0.10 0.100.10 0.10 H₂O [vol. %] 0.10 0.10 0.10 0.10 49.95 49.95 49.95 49.95 99.8099.80 99.80 99.80 N₂ [vol. %] 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 H₂ [vol. %] — — — — — — — — — — — — H₂O/CO₂ feed ratio 0.0010.001 0.001 0.001 1 1 1 1 998 998 998 998 Conversion conditions Pressure[bara] 10 10 1 1 10 10 1 1 10 10 1 1 Temp. [° C.] 1200 1090 1200 10901200 1090 1200 1090 1200 1090 1200 1090 Composition of CO/H2-containingstream CO [vol. %] 99.1 97.6 99.7 99.7 74.45 73.35 74.83 74.78 49.7 49.249.85 49.81 H₂O [vol. %] — — — — 0.4 0.9 0.1 0.1 0.6 1.2 0.16 0.19 N₂[vol. %] 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 H₂[vol. %] 0.05 0.05 0.05 0.05 24.5 24.1 24.9 24.9 48.8 47.7 49.86 49.77CO₂ [vol. %] 0.8 2.3 0.2 0.2 0.4 1.3 0.11 0.14 0.24 0.6 0.06 0.09 CH₄[vol. %] — — — — 0.20 0.30 0.01 0.03 0.61 1.25 0.02 0.09 H₂/CO ratio ofsyngas 1.01 1.04 1.00 1.00 1.68 1.72 1.67 1.67 3.02 3.09 3.00 3.01stream

That which is claimed is:
 1. A method for producing a syngas stream, themethod at least comprising the steps of: (a) providing ahydrocarbon-containing stream; (b) providing a reactor containing aheated mass of solids at a temperature of at least 1000° C.; (c)cracking the hydrocarbon-containing stream provided in step (a) in thereactor containing the heated mass of solids provided in step (b),thereby at least obtaining C and H₂; (d) removing an H₂-containingstream from the reactor; (e) converting the C obtained in step (c) inthe reactor by feeding a CO₂-containing stream and steam to the reactorat an H₂O/CO₂ vol. % feed ratio of greater than 0.0001, therebyobtaining a CO/H₂-containing stream; (f) removing the CO/H₂-containingstream from the reactor; (g) combining the H₂-containing stream removedin step (d) with the CO/H₂-containing stream removed in step (f) therebyobtaining a syngas stream having a H₂/CO vol. % ratio of at least 1.0and below 3.1.
 2. The method according to claim 1, wherein thehydrocarbon-containing stream provided in step (a) comprises at least 10ppm mercaptans.
 3. The method according to claim 1, wherein thehydrocarbon-containing stream provided in step (a) comprises at least1.0 vol. % olefins.
 4. The method according to claim 1, wherein thereactor containing the heated mass of solids is in step (c) at atemperature of at least 1100° C.
 5. The method according to claim 1,wherein the H₂-containing stream removed from the reactor in step (d)comprises at least 1 ppm H₂S, which is at least partially removed beforecombining in step (g).
 6. The method according to claim 1, wherein apart of the H₂-containing stream removed from the reactor in step (d) isused to heat the reactor.
 7. The method according to claim 1, whereinthe reactor containing the heated mass of solids is in step (e) at atemperature of at least 1000° C.
 8. The method according to claim 1,wherein in step (e) the C obtained in step (c) is converted in thereactor at an H₂O/CO₂ vol. % feed ratio of at least 0.9 and at most1000.
 9. The method according to claim 1, wherein the syngas streamobtained in step (g) has a H₂/CO vol. % ratio of at least 1.75 and atmost 2.2.